US4824651A - Process for preparing silicon carbide fibers - Google Patents

Process for preparing silicon carbide fibers Download PDF

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Publication number
US4824651A
US4824651A US07/158,801 US15880188A US4824651A US 4824651 A US4824651 A US 4824651A US 15880188 A US15880188 A US 15880188A US 4824651 A US4824651 A US 4824651A
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formula
compound
range
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US07/158,801
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Volker Frey
Bernd Pachaly
Norbert Zeller
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Wacker Chemie AG
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Wacker Chemie AG
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Assigned to WACKER-CHEMIE GMBH reassignment WACKER-CHEMIE GMBH ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: FREY, VOLKER, PACHALY, BERND, ZELLER, NORBERT
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/58—Metal-containing linkages

Definitions

  • the present invention relates to silicon carbide fibers and more particularly to a process for preparing silicon carbide fibers.
  • Silicon carbide fibers and processes for preparing silicon carbide fibers from organometallic polymers are well known. These fibers are prepared from polysilanes, polycarbosilanes or polysilazanes. The processes for preparing silicon carbide fibers all have a common feature of spinning a suitable polymer with subsequent pyrolysis under an inert gas or in vacuo.
  • R represents the same or different alkyl, alkenyl or aryl radicals and R 1 represents the same or different alkyl radicals, which may optionally be mixed with a compound of the formula
  • R is the same as above and R 2 represents a methoxy radical or is the same as R, in the presence of at least one compound of the formula
  • R 1 is the same as above, R 3 is the same or different alkenyl radicals, x is in the range of from 0.5 to 1.5, y is in the range of from 3 to 5 and n is in the range of from 500 to 2,000, into fibers and thereafter reacting the fibers under an inert atmosphere or in vacuo at temperatures in the range of from 800° to 1,300° C.
  • the copolymer is obtained by reacting at least one disilane of the formula
  • R and R 1 are the same as above, which may optionally be mixed with a compound of the formula
  • R is the same as above and R 2 represents a methoxy radical or is the same as R, in the presence of at least one compound of the formula
  • R 1 is the same as above
  • R 3 is the same or different alkenyl radicals
  • x is in the range of from 0.5 to 1.5
  • y is in the range of from 3 to 5
  • n is in the range of from 500 to 2,000
  • R 1 and R 3 are the same as above, a is in the range of from 0.3 to 0.5, b is in the range of from 0.01 to 0.1, c is in the range of from 0.5 to 0.7, d is in the range of from 10 to 100, e is in the range of from 500 to 600 and f is in the range of from 1 to 1,000.
  • the copolymer which is spun into fibers is obtained by reacting at least one disilane of the formula
  • R 1 , R 3 , a, b, c, d, e and f are the same as above, may be added to form the copolymer.
  • Alkyl groups represented by R, R 1 and R 2 each preferably contain 1 to 12 carbon atoms per radical, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, 2-ethylhexyl and dodecyl radicals.
  • aryl radicals represented by R and R 2 are the phenyl radical and xenyl radical.
  • the methyl radical is the preferred alkyl radical represented by R, R 1 and R 2 because of its availability.
  • the most important example of an alkenyl radical represented by R and R 3 is the vinyl radical.
  • the tert-butyl radical is another example of a radical represented by R in the compound of the formula
  • the alkali metal can be lithium, sodium, potassium, rubidium or cesium.
  • Sodium and potassium are the preferred alkali metals in the compound of the formula
  • Examples of preferred disilanes are 1,1,2-trimethyl-1,2,2-trimethoxydisilane, 1-phenyl-1,2-dimethyl-1,2,2-trimethoxydisilane and 1-vinyl-1,2-dimethyl-1,2,2-trimethoxydisilane.
  • the most important example of a compound of the formula is 1,1,2-trimethyl-1,2,2-trimethoxydisilane, 1-phenyl-1,2-dimethyl-1,2,2-trimethoxydisilane and 1-vinyl-1,2-dimethyl-1,2,2-trimethoxydisilane.
  • dimethylmethoxysilane and diphenylmethylsilane are dimethylmethoxysilane and diphenylmethylsilane.
  • disilanes is preferably used in an amount of from 0.5 to 5 percent by weight, preferably from 2 to 4 percent by weight, based on the weight of the disilanes employed.
  • the catalyst is used as a catalyst; therefore, it is preferably used in an amount of from 0.2 to 0.5 percent by weight, based on the weight of the disilanes.
  • R 1 is a methyl radical
  • R 3 is a vinyl radical
  • x is in the range of from 0.5 to 1.5
  • y is in the range of from 3 to 5
  • n is in the range of from 500 to 2,000.
  • R represents the same or different alkyl, alkenyl or aryl radicals and R 1 represents the same or different monovalent alkyl groups, which may optionally be mixed with a compound of the formula
  • R is the same as above and R 2 represents a methoxy radical or R, in the presence of at least one compound of the formula
  • R 1 is the same as above, R 3 represents the same or different alkenyl radicals, x is in the range of from 0.5 to 1.5, y is in the range of from 3 to 5 and n is in the range of from 500 to 2,000, is carried out after the reactants and catalyst have been mixed at temperatures of preferably from 25° C. to 220° C., and is discontinued when no additional monomeric organomethoxysilane is distilled off.
  • This reaction is preferably carried out under the pressure of the surrounding atmosphere, that is to say, under 1,020 hPa (absolute) or about 1,020 hPa (absolute).
  • R 1 is a methyl radical
  • R 3 is a vinyl radical
  • a is in the range of from 0.3 to 0.4
  • b is in the range of from 0.01 to 0.1
  • c is in the range of from 0.5 to 0.7
  • d is in the range of from 10 to 100.
  • R 1 is a methyl, radical
  • R 3 is a vinyl radical and e is in the range of from 500 to 600.
  • R 1 is a butyl radical and f is in the range of from 1 to 1,000.
  • the copolymer of this invention is obtained by mixing at least one disilane of the formula
  • R and R 1 are the same as above, which may optionally be mixed with a compound of the formula
  • R 1 , R 3 , a, b, c, d, e and f are the same as above, and then reacting the mixture at temperatures of preferably from 50° C. to 150° C. in the presence of an organic solvent.
  • This reaction is preferably carried out under the pressure of the surrounding atmosphere, that is to say, under 1,020 hPa (absolute) or about 1,020 hPa (absolute).
  • organic solvents which may be employed are organic, aromatic or aliphatic hydrocarbons. Specific examples of solvents which may be used are toluene, xylene or petroleum ether having various boiling fractions.
  • the silicon carbide fibers of this invention are obtained by known spinning processes, such as dry spinning, wet spinning or melt spinning, and more preferably by the melt spinning process.
  • fibers having an average diameter of 5 to 50 um are spun from the melt and are crosslinked by heat, light, such as, for example, UV light, steam and/or atmospheric oxygen.
  • the non-fusible fibers are bundled to a fiber bundle of 10 to 1,000 individual threads (filaments) and reacted in a tubular oven at a temperature of from 800° to 1,300° C., and more preferably from 1,050° to 1,150° C., under an inert atmosphere, such as obtained, for example, by a blanket of an inert gas, such as argon or nitrogen, or in vacuo.
  • the tensile strength of the silicon carbide fibers obtained according to this invention is 300 N/mm 2 for a 50 um thread and 3,000 N/mm 2 for a 10 um thread.
  • Silicon carbide fibers are generally used in fiber composites, preferably metals, such as aluminum and titanium, or ceramic materials, such as silicon carbide.
  • This polymer was spun in a melt spinning device with a 300 um jet at 120° C. under an argon pressure of 10 bar, the take-off speed being 60 m/minute. On discharge from the spinning jet, the fibers were blue-gray and were not transparent. The fibers were then passed through a heating zone 30 cm long (temperature about 100° C.) and past a UV source, whereupon they became colorless and transparent. The fibers thus obtained showed good tear strength and flexibility and were bundled to a yarn of 50 filaments.
  • This fiber bundle was heated up to 1,300° C. in a tubular oven blanketed with argon under a tensile stress of 50 g/mm 2 . After being kept at 1,300° C. for 30 minutes, the fibers were withdrawn from the oven. The weight loss on pyrolysis was 18 to 20 percent by weight. The fibers are glossy black and have good flexibility and a tensile strength of a maximum of 2,700 N/mm 2 with an average diameter of 10 to 20 um.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Silicon Polymers (AREA)
  • Inorganic Fibers (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
  • Ceramic Products (AREA)
US07/158,801 1987-03-06 1988-02-22 Process for preparing silicon carbide fibers Expired - Fee Related US4824651A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873707225 DE3707225A1 (de) 1987-03-06 1987-03-06 Verfahren zur herstellung von siliciumcarbidfaser
DE3707225 1987-03-06

Publications (1)

Publication Number Publication Date
US4824651A true US4824651A (en) 1989-04-25

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Country Status (6)

Country Link
US (1) US4824651A (de)
EP (1) EP0281964B1 (de)
JP (1) JPS63243327A (de)
AT (1) ATE58761T1 (de)
CA (1) CA1290518C (de)
DE (2) DE3707225A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5130400A (en) * 1989-06-01 1992-07-14 Wacker-Chemie Gmbh Process for preparing spherical, monodispersed organopolysiloxanes or silicon oxycarbides
US5250646A (en) * 1990-11-20 1993-10-05 Wacker-Chemie Gmbh Process for the preparation of metallopolysilanes, and their use
US20100168309A1 (en) * 2007-05-01 2010-07-01 Mackinnon Iain A Polymer And Polymer Compositions

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5025075A (en) * 1988-07-22 1991-06-18 Dow Corning Corporation Methylpolysilanes and method for their preparation
US5023307A (en) * 1988-07-22 1991-06-11 Dow Corning Corporation Methylpolysilanes having controllable rheology and method for their preparation
US4889904A (en) * 1988-07-22 1989-12-26 Dow Corning Corporation Process for the preparation of methylpolysilanes having controlled carbon content
US5171722A (en) * 1991-10-09 1992-12-15 University Of Florida SiC fibers having low oxygen content and methods of preparation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0023096A1 (de) * 1979-06-28 1981-01-28 Ube Industries Limited Organometallische Copolymere, Verfahren zu ihrer Herstellung und hieraus erhaltene Formkörper eines anorganischen Carbids
US4497787A (en) * 1982-03-23 1985-02-05 Union Carbide Corporation Branched polycarbosilanes and their use in the production of silicon carbide
US4631179A (en) * 1985-05-28 1986-12-23 Ethyl Corporation Process for the production of silicon carbide by the pyrolysis of a polycarbosilane polymer

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1551342A (en) * 1924-02-25 1925-08-25 Gen Electric Method of manufacturing turbine wheels, nozzle diaphragms, and the like
JPS6028927B2 (ja) * 1975-06-11 1985-07-08 東北大学金属材料研究所長 シリコンカ−バイド繊維の製造方法
JPS51147623A (en) * 1975-06-11 1976-12-18 Res Inst Iron Steel Tohoku Univ A process for manufacturing silicon carbide fibers with high strength
US4100233A (en) * 1975-04-25 1978-07-11 The Research Institute For Iron, Steel And Other Metals Of The Tohoku University Silicon carbide fibers having a high strength and a method for producing said fibers
GB2009196B (en) * 1977-10-26 1982-04-15 Res Inst For Special Inorganic Polycarbosilane process for its prudiction and its use as material for producing silicon carbide
JPS6046131B2 (ja) * 1980-11-11 1985-10-14 宇部興産株式会社 ポリカルボシランの製造法
JPS599220A (ja) * 1982-06-30 1984-01-18 Shin Etsu Chem Co Ltd 炭化けい素繊維の製造方法
US4546163A (en) * 1984-09-04 1985-10-08 Dow Corning Corporation Silicon carbide preceramic vinyl-containing polymers
JPS61295298A (ja) * 1985-06-21 1986-12-26 Nippon Carbon Co Ltd 窒化ケイ素の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0023096A1 (de) * 1979-06-28 1981-01-28 Ube Industries Limited Organometallische Copolymere, Verfahren zu ihrer Herstellung und hieraus erhaltene Formkörper eines anorganischen Carbids
US4497787A (en) * 1982-03-23 1985-02-05 Union Carbide Corporation Branched polycarbosilanes and their use in the production of silicon carbide
US4631179A (en) * 1985-05-28 1986-12-23 Ethyl Corporation Process for the production of silicon carbide by the pyrolysis of a polycarbosilane polymer

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5130400A (en) * 1989-06-01 1992-07-14 Wacker-Chemie Gmbh Process for preparing spherical, monodispersed organopolysiloxanes or silicon oxycarbides
US5250646A (en) * 1990-11-20 1993-10-05 Wacker-Chemie Gmbh Process for the preparation of metallopolysilanes, and their use
US20100168309A1 (en) * 2007-05-01 2010-07-01 Mackinnon Iain A Polymer And Polymer Compositions
US20100168325A1 (en) * 2007-05-01 2010-07-01 Gough Helen L Polymer Compositions
US8481640B2 (en) 2007-05-01 2013-07-09 Dow Corning Corporation Polymer compositions
US8592545B2 (en) 2007-05-01 2013-11-26 Dow Corning Corporation Polymer and polymer compositions

Also Published As

Publication number Publication date
JPH0213045B2 (de) 1990-04-03
DE3861139D1 (de) 1991-01-10
CA1290518C (en) 1991-10-15
ATE58761T1 (de) 1990-12-15
DE3707225A1 (de) 1988-09-15
EP0281964A1 (de) 1988-09-14
JPS63243327A (ja) 1988-10-11
EP0281964B1 (de) 1990-11-28

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